WO2008024016A1

WO2008024016A1 - Hydrocarbon processing method

Info

Publication number: WO2008024016A1
Application number: PCT/RU2007/000067
Authority: WO
Inventors: Aleksey Anatolievich Ozerenko; Vladimir Vasilievich Zamanov
Original assignee: Aleksey Anatolievich Ozerenko
Priority date: 2006-08-18
Filing date: 2007-02-09
Publication date: 2008-02-28
Also published as: RU2312127C1

Abstract

The invention relates to chemical production methods, in particular to producing different types of hydrocarbon fuels and initial hydrocarbon products for main and petrochemical synthesis from such sources of raw material as crude oil, high-boiling oil fractions, oil residues, products of coal liquefaction and of coke and by-product processing, waste oils and from domestic and industrial organic wastes. The inventive hydrocarbon processing method consists in selecting and/or synthesising hydrogen donors, in mixing hydrocarbons, hydrogen and a catalyst, in hydrogenating the thus obtained mixture, in separating it, in extracting light and heavy fractions and, afterwards, in conveying the heavy fraction with the catalyst and selected hydrogen donors to a mixing stage, in hydrogenating the light fraction and in extracting the synthesised hydrogen donors for sending them to the mixing stage.

Description

A method of processing hydrocarbons.

The present invention relates to chemical technology, in particular to a technology for producing raw materials from such sources as crude oil, high boiling oil fractions, oil residues, coal liquefaction products and by-product coke production, waste oils, household and industrial organic wastes of various types of hydrocarbon fuels and hydrocarbon feedstocks for basic and petrochemical synthesis.

For the aforementioned field of chemical technology, various hydrocarbon processing methods are known based on the principles of hydrogenation and dehydrogenation of processed hydrocarbons.

A known method of processing hydrocarbons, comprising the step of mixing hydrocarbons with a hydrogen-containing gas, hydrogenating the resulting mixture, separating it, isolating a fraction containing light oil products (see RF patent N “2241735 IPC ⁷ C10G63 / 02, published October 12, 2004).

The disadvantage of this method is that it requires an increased pressure of a hydrogen-containing gas, since hydrogenation is due to molecular hydrogen. In addition, many hydrocarbons have a dense structure, which virtually eliminates the penetration of hydrogen into this structure for hydrogenation.

SUBSTITUTE SHEET (RULE 26) A known method of processing hydrocarbons, including the selection or synthesis of a donor-hydrogen solvent, the stage of mixing hydrocarbons with a donor-hydrogen solvent, hydrogenation of the resulting mixture, its separation, separation of the fraction containing light oil products (see US patent N ° 4329221 NCI 208/214, published 11.05 .1982).

The known method solves the technical problem - the penetration of hydrogen into the structure of the processed hydrocarbon for its hydrogenation. However, in this method, the hydrogen donor solvent does not transfer hydrogen sufficiently to the hydrogen acceptor, since the hydrogen donor is not activated.

This disadvantage is eliminated in the known method, which is closest to the present invention, namely, a method for processing hydrocarbons, including the selection and / or synthesis of hydrogen donors, the stage of mixing hydrocarbons, hydrogen donors and catalyst, hydrogenation of the mixture, its separation, the allocation of light and heavy fractions, (see RF patent XQ 2255959 IPC ⁷ C10G47 / 02, published July 10, 2005).

The disadvantage of this method is that it does not fully provide deep processing of heavy high molecular weight raw materials into light petroleum products and other petrochemical synthesis products due to the lack of an optimal ratio between the hydrogen donor and

SUBSTITUTE SHEET (RULE 26) hydrogen acceptor during hydrogenation, as well as insufficiently high degree of mixing of such hydrocarbons with the catalyst before hydrogenation.

In view of the foregoing, the present invention solves the technical problem of ensuring the optimal ratio in hydrocarbons between a hydrogen donor and a hydrogen acceptor during hydrogenation and increasing the degree of mixing of hydrocarbons with a catalyst before hydrogenation.

The problem is solved due to the fact that in the known method of hydrocarbon processing, including the selection and / or synthesis of hydrogen donors, the stage of mixing hydrocarbons, hydrogen donors and a catalyst, hydrogenation of the mixture, its separation, separation of light and heavy fractions, heavy fraction together with the catalyst and the selected hydrogen donors are sent to the mixing stage, and the light fraction is subjected to hydrogenation, followed by the release of the synthesized hydrogen donors, which are sent to the transfer stage sewing.

And also due to the fact that:

- the light fraction is selected with a boiling point up to 180 - 420 ⁰ C;

- the heavy fraction is selected with a boiling point above 180 - 420 ⁰ C;

- hydrogen donors are selected in the form of their own fractions

SUBSTITUTE SHEET (RULE 26) hydrocarbons with a boiling point of 200 - 400 ⁰ C; hydrogen donors synthesize from their own fractions of hydrocarbons, with a boiling point of 200 - 400 ⁰ C;

- as the hydrogen donors, the hydro derivatives of bi- and tricyclic aromatic hydrocarbons and their alkyl derivatives are selected and / or synthesized;

- as a catalyst, water-soluble compounds of metals of the VI and VIII groups of elements of the Periodic system are selected;

- as a catalyst, water-soluble or gel-like silicon compounds in the amount of OD - 5.0 weight are selected. % by weight of hydrocarbons;

- hydrogenation of hydrocarbons is carried out at a pressure of 1.0 to 7.0 MPa and a temperature of 350 to 500 ⁰ C;

The hydrocarbon processing method is illustrated in the flowchart in the figure.

As follows from the figure, the hydrocarbons together with the water contained in them are sent for processing through product pipeline 1 to mixer 2. In mixer 2, hydrocarbons are mixed with hydrogen donors and a catalyst in the form of water-soluble compounds of metal salts or water-soluble / gel-like silicon compounds. Hydrogen donors are selected in the form of their own fractions of hydrocarbons with

SUBSTITUTE SHEET (RULE 26) boiling point 200 - 400 ⁰ C and / or obtained from own fractions of hydrocarbons, with a boiling point 200 - 400 ⁰ C.

After mixing, the resulting mixture through product pipeline 3 enters the dispersant 4. In the dispersant 4 is dispersed, including the catalyst, to a finely dispersed state of the emulsion or suspension, with a particle size of up to 10 - 50 microns. After dispersion, the mixture through product pipeline 5 enters the reactor 6, where hydrogenation and / or cracking of the resulting mixture is carried out.

In the reactor 6, when heated, due to the explosive transition of the catalyst solution into the vapor phase, the formation of a catalytic system that provides hydrogenation and / or cracking occurs. The resulting products through product pipeline 7 enter the column — separator 8 for separation into fractions, light, with a boiling point up to 180 - 420 ⁰ C and a heavy fraction, with a boiling point above 180 - 420 ⁰ C It should be noted that the catalyst is always in heavy fraction. After separation, the heavy fraction through product line 9 is sent to the mixer 2. The light fraction through line 10 is fed to the hydrogenation reactor 11.

In the reactor 11, the light fraction is hydrogenated in the presence of a hydrogenation catalyst. As catalysts, for example, stationary alumina-cobalt-molybdenum and / or alumina-nickel-molybdenum catalysts are selected. Such hydrogenation

SUBSTITUTE SHEET (RULE 26) b provides both the necessary quality of marketable products and the formation of hydrogen donors, while it is possible to obtain hydro derivatives of bi- and tricyclic aromatic hydrocarbons and their alkyl derivatives.

After hydrogenation, the resulting mixture through product line 12 is sent to a distiller 13, where commercial products, such as gasoline, diesel fuel, etc. and a hydrogen donor, are released. The selected hydrogen donor through the product pipe 14 enters the mixer 2.

Since hydrogen donors are solvents with respect to the more viscous fractions of the processed hydrocarbons, they dissolve the hydrocarbons in mixer 2. Dissolving the hydrocarbons in mixer 2 and lowering the viscosity leads to more efficient incorporation of the catalyst into the processed mixture, which, in turn, provides more efficient hydrogenation and / or further cracking of hydrocarbons.

The use of hydrogen donors derived from processed hydrocarbons suggests a greater chemical affinity for the hydrogen acceptors of the original hydrocarbons. This makes it possible to control the process, stabilize it, and optimize the production of light fuels and basic products for petrochemical synthesis.

Since the heavy fraction and the catalyst are fed to the mixing stage, once introduced the catalyst is recycled with heavy

SUBSTITUTE SHEET (RULE 26) fractions of hydrocarbons, ensuring the occurrence of hydrogenation and / or cracking reactions. Hydrogen donors contained in hydrocarbons after mixing (when there is a lack of intrinsic hydrogen donors, they are produced by hydrogenation of the light fraction), mainly in the form of hydro derivatives of bi- and tricyclic aromatic hydrocarbons and their alkyl derivatives, they transfer hydrogen to acceptors, stabilize radical products resulting from degradation hydrocarbon multimer. In this case, a low hydrogen pressure is required, which is sufficient for the deep conversion of hydrocarbons into light petroleum products or products for petrochemical synthesis.

On the other hand, the multiple return of the catalyst together with hydrogen donors to the mixing stage, as experience shows, increases the catalytic efficiency of the catalytic system.

Some examples of the method, illustrating but not limiting it:

Example 1. Gas condensation is subjected to hydrogenation. The feedstock contained fractions with boiling points: n.a. - 180 ° C - 40%,

180 - 300 ⁰ C - 55%, above 300 ⁰ C - 5%

SUBSTITUTE SHEET (RULE 26) and mixed with 0.1 to 5.0% silicate water-soluble catalyst and

30% of recycle fractions boiling above 18O ⁰ C. The reaction was carried out at 410 - 450 ⁰ C and pressure up to 3.0 MPa in a hollow reactor. As a result, 95% of A-80 gasoline and 5.0% of Cj - C ₄ gases were obtained, as well as 30% of fractions boiling above 180 ⁰ C and used as recycle. In this recycle contained up to 95% of the introduced catalyst and hydrogen donors. Fresh catalyst at 15 times recirculation was not introduced.

Example 2. Hydrogenation is subjected to crude West Siberian oil.

The feedstock contained fractions with boiling points: n.a. - 180 ° C - 18.6%,

180 - 350 ° C - 36.9%,

350 - 500 ° С - 14.3%, above 500 ° C - 29.7%, losses - 0.5% and mixed with 29% of the hydrogenated fractions boiling above 35O ⁰ C, as well as 0.01 - 1.0 % water soluble salt of molybdenum. The reaction was carried out at 410 - 45O ⁰ C and pressure up to 5.0 MPa in a hollow reactor. 34% of gasoline, 60.5% of diesel fuel, 5.5% of gas and 29% of fractions boiling above 350 ^° C were obtained, used as recirculate containing up to 95% of the catalyst and hydrogen donors.

SUBSTITUTE SHEET (RULE 26) Fractions boiling up to 35O ⁰ C were subjected to hydrofining by known methods with the production of AI-93 gasoline (95) and diesel fuel meeting the European standard UCO-4 requirements and used as commercial products.

Example 3. Hydrogenation is subjected to the distillate of vacuum distillation of fuel oil.

Raw materials boiling at temperatures up to 500 ⁰ C were mixed with 35% of the hydrogenated fractions boiling above 340 ⁰ C and 0.1-5% of a water-soluble silicate catalyst. The reaction was carried out at 410 - 450 ⁰ C and pressure up to 2.5 MPa in a hollow reactor. 93% of the boiling fractions up to 34O ⁰ C, 7% of gas and 35% of the boiling fractions above 34O ⁰ C were obtained. They were used as recycle containing up to 95% of the catalyst and hydrogen donors.

Fractions boiling up to 340 ⁰ C were subjected to hydrofining by known methods to obtain 37.8% of AI-93 gasoline (95) and 53.8% of diesel fuel meeting the requirements of UCO-4 European standard and used as commercial products.

Example 4. Hydrogenation is subjected to a residue of vacuum distillation of fuel oil.

Raw materials boiling at temperatures above 500 ⁰ C were mixed with 20% fractions of hydrogenizate boiling above 340 ⁰ C and containing hydrogen donors, as well as 0.01 - 1.0% water-soluble molybdenum salt. Reaction

SUBSTITUTE SHEET (RULE 26) carried out in a hollow reactor at a temperature of 410 - 450 ° C and pressure

7.0 MPa. 7% of gas and 43% of fractions boiling up to 340 ⁰ C, 25% of fractions boiling within 340 - 460 ⁰ C and 25% of fractions boiling at temperatures above 460 ⁰ C and used as recycle were obtained.

Fractions 340 - 460 ⁰ C are subjected to catalytic cracking according to the technology described in example 3. Cracking products together with a fraction up to 340 ⁰ C are subjected to hydrofining by known methods. As a result, with the full processing of the tar, 23% of gasoline and 60% of diesel fuel were obtained, which meet the requirements of UCO - 4 European standard.

Thus, the formation of a catalytic system with the participation of feed hydrocarbons, the formation of hydrogen donors from feed hydrocarbons and their return to the mixing stage leads to a new qualitative effect - the possibility of processing a wide range of hydrocarbons to produce valuable marketable products.

SUBSTITUTE SHEET (RULE 26)

Claims

Claim

1. A method of processing hydrocarbons, including the selection and / or synthesis of hydrogen donors, the stage of mixing hydrocarbons, hydrogen donors and a catalyst, hydrogenation of the resulting mixture, its separation, separation of light and heavy fractions, characterized in that the heavy fraction together with the catalyst and selected hydrogen donors sent to the mixing stage, and the light fraction is subjected to hydrogenation, followed by the release of synthesized hydrogen donors, which are sent to the mixing stage.

2. The method according to p. 1 characterized in that the light fraction is selected with a boiling point up to 180 - 420 ⁰ C;

3. The method according to p. 1 characterized in that the heavy fraction is selected with a boiling point above 180 - 420 ⁰ C;

4. The method according to p. 1 characterized in that the hydrogen donors are selected in the form of their own fractions of hydrocarbons with a boiling point of 200 - 400 ⁰ C;

5. The method according to p. 1 characterized in that the hydrogen donors synthesize from their own fractions of hydrocarbons, with a boiling point of 200 - 400 ⁰ C;

SUBSTITUTE SHEET (RULE 26)

6. The method according to p. 1 characterized in that as a hydrogen donor choose and / or synthesize hydro-derivatives of bi- and tricyclic aromatic hydrocarbons and their alkyl derivatives;

7. The method according to p. 1 characterized in that as a catalyst choose water-soluble compounds of metals of groups VI and VIII of the elements of the Periodic system;

8. The method according to p. 1 characterized in that the catalyst is selected water-soluble or gel-like silicon compounds in an amount of 0.1 to 5.0 weight. % by weight of hydrocarbons;

9. The method according to p. 1 characterized in that the hydrogenation of hydrocarbons is carried out under a pressure of 1.0 to 7.0 MPa and a temperature of 350 to 500 ⁰ C;

SUBSTITUTE SHEET (RULE 26)